Process for isolating cis-1,4-polyisoprene from hydrocarbon solutions



United States Patent Oflice 3,544,542 Patented Dec. 1, 1 970 3,544,542 PROCESS FOR ISOLATING CIS-1,4-POLYISOPRENE FROM HYDROCARBON SOLUTIONS Josef Witte, Cologne-Stammheim, Gottfried Pampus, Leverkusen, Friedrich Haas, Cologne-Buchheim, and Nikolaus Schtin and Egon Kuntz, Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Nov. 26, 1968, Ser. No. 779,210 Claims priority, application Germany, Dec. 21, 1967, 1,720,763 Int. Cl. C08d 5/00; C08f 1/92, 27/00 US. Cl. 26094.7

ABSTRACT OF THE DISCLOSURE Improved process for isolating cis-l,4-polyisoprene from its solution in organic solvents wherein the catalyst is deactivated by means of a primary or secondary aliphatic diamine or polyamine, optionally in combination with a lower aliphatic alcohol and/or a secondary aliphatic or cycloaliphatic monoamine.

It is known that isoprene can be polymerised by means of organometallic mixed catalysts of the Ziegler type to give a product with a structure resembling that of natural rubber and having predominantly cis-1,4-linkages. Vulcanisates of these polyisoprenes differ from corresponding natural rubber vulcanisates, however, so far as their properties in critical fields of application are concerned. Natural rubber is superior to commercial cis-l,4- polyisoprene in its degree of crosslinking and network structure, as reflected in both the tensile strength and structural strength of the vulcanisates, quite apart from their higher strain values. This applies, in particular, to vulcanisates which contain no or small amounts of fillers, especially weak fillers, such as MT-carbon blacks, and is less pronounced, but nevertheless still recognisable, in HAF- and ISAF-carbon black mixtures of tread quality for vehicle tires.

The polymerisation of isoprene with organometallic mixed catalysts, for example Al(iso-C H /TiCl is usually carried out in solution in solvents, for example aliphatic or aromatic hydrocarbons, such as pentane, hexane,

cyclohexane, benzene or toluene. An example for this type of polymerisation is as follows: The polymerisation catalyst is added to an 8-30% by weight solution of isoprene in the absence of oxygen and moisture. For example, mixtures of aluminum trialkyls, optionally in admixture with their etherates and titanium tetrachloride, are used as the catalysts. Polymerisation may be carried out at temperatures of from 20 to +80 C. After the required monomer conversion, for example 90% or more, has been reached, the catalyst is inactivated by the addition of suitable substances, for example alcohols such as methanol or ethanol. Following the addition of suitable stabilisers, for example 2,6-di-tert.-butyl-4-methylphenol; 2.2'-dihydroxy-3,3'-di-tert.-butyl-5,5' dimethyl diphenyl methane; or phenyl-B-naphthylamine, the polymer can be isolated from the solution by'the addition of a precipitant, for example ethanol or acetone. On a commercial scale, polyisoprene is recovered from the hydrocarbon solution (stripping). The rubber, which is isolated in the form of crumbs, is dried in a vacuum cabinet ether on a belt conveyor or by means of a screw.

The isolation of cis-1,4-po1yisoprene from solution in hydrocarbons by steam distillation (stripping) is accom- Claims 4 panied by greater degradation of the polymer than is observed on precipitation with ethanol. This is reflected in a slight reduction in the Mooney viscosty (ML-4/ 100 C.,) and to a greater extent in marked reduction in the Defo hardness. It is not possible to prevent this degradation by increasing the concentration of the stabiliser. However, it is undesirable that there should be any degradation in the recovery stage, because further processing of the cis-l,4-polyisoprene, for example compounding on mixing rollers or in internal mixers, is inevitably accompanied by further degradation.

In compounding cis-l,4-polyisoprene a molecular weight as high as possible, i.e. very high Mooney and Defo values, is desirable because distribution of the filters and vulcanisation auxiliaries is better and considerably more uniform. This is caused by a higher shear gradient in the high molecular weight polymers. Better distribution of the fillers results accordingly in improved vulcanisates.

The present invention relates to an improved process for isolating cis-l,4-polyisoprene from catalyst-containing solutions thereof in organic solvents by deactivating the catalyst followed by steam distillation, optionally in the presence of a stabiliser, which comprises deactivating the catalyst by adding a primary or secondary aliphatic diamine or polyamine to the cis-l,4-polyisoprene solution in a quantity of from 0.02 to 1.00% by weight, based on solid rubber, optionally in admixture with a lower aliphatic alcohol in a quantity, of from 0 to 5% by weight and/ or a secondary aliphatic or cycloaliphatic monoamine containing at least 10 carbon atoms, in a quantity of from 0 to 0.8% by weight, based on solid rubber. The deactivating agents may be added, either separately or in admixture, in solution in a hydrocarbon, preferably in the polymerisation medium.

Primary or secondary diamines and polyamines suitable for use in the process according to the invention include in particular dior polyalkyl amines, preferably those wherein the alkyl moities contnain up to 6 carbon atoms, for example 1,2-diamino ethane; 1,2-di-(methylamino)-ethane; bis-(2-aminoethyl)-amine; 1,11-diamino- 3,6,9-triazo-undecane; 1,3-diaminopropane; bis(3-amino propyl)-amine; and methyl-bis-(3-aminopropyl)-amine.

Dior polyalkyl amines (for example with from 3 to 5 amino groups) in which the amino groups are separated by 2 or 3 methylene groups, may also be used with advantage in the process according to the invention. It is also possible, however, to use amines with longer alkyl chains, for example, with C -C chains, such as hexamethylene diamine, or tetramethylene diamine.

Although the secondary monoamines, which may optionally be used, do not on their own show any activity during working-up by distillation with steam, they nevertheless intensify the effect of the primary or secondary diamines of polyamines, and improve the properties of the vulcanisate obtained from the crude rubber. They are used in quantities of up to 0.8% by weight, based on solid rubber, and preferably in quantities of at least 0.05% by weight.

Suitable amines include, in particular, aliphatic or cycloaliphatic amines containing one fairly long chain and one shorter alkyl or cycloalkyl radcal. Derivatives of methylamine in which one of the hydrogen atoms is replaced by a linear or branched alkyl radical with from 9 to 24 carbon atoms, are particularly preferred. Di-2- ethylhexylamine, dicyclohexylamine, and N-stearlymethyl-amine are examples of suitable amines. The amine is preferably used in a quantity of from 0.2 to 0.7% by weight, based on solid rubber.

. hexane (based on solid rubber) was. added to other com- -The-dior polyamines are used in quantities of from 0.02 to 1.0% by weight, and preferably in quantities of from 0.05 to 0.5% by weight, based on solid rubber.

Methanol, ethanol or isopropanol may, for example, be usedas the lower aliphatic alcohols, in quantities of pletely identical polymerisation mixtures, which were then stabilised with 1% by weight of 2,6-di-tert.-butyl-4-methylphenol. The amines were used in amounts providing equivalent quantities of amino nitrogen.

this polymerisation mixture (conversion 93%=9.3%

solids content) at 20 C. to deactivate the catalyst and for the purpose of stabilisation.

A mixture of a dior polyfunctional amine and 2.5%

up to 5% by weight, and preferably, in quantities of at 5 The polyisoprene solutions were divided, the solid rubleast 0.05% by weight, based on solid rubber. her being isolated from the resulting solutions by precipi- The amines or the mixture of the two amines may be tation with alcohol and by distillation with steam. The diluted with a hydrocarbon, preferably the hydrocarbon rubber was dried in vacuo at 50 C. used as polymerisation medium, so that a homogeneous Table 1 shows the solution viscosity, Mooney and Defo solution is obtained. The alcohols are used in particular values of the polyisoprenes isolated by precipitation with if difiiculties are involved in dissolving the amines. alcohol and distillation with steam, in dependence upon Working-up itself, i.e. steam, distillation, may be carthe type of amine used and the quantity in which it is ried .out in the usual way, following the addition of the used. v deactivator mixture used according to the invention. As A=working-up by precipitation with ethanol. a rule, conventional stabilisers and anti-agers are added, B=working-up by steam distillation.

TABLE 1 Solution Quantity, Defo viscosity percent ML-4 H/E in toluene Amine by weight 100 C. 80 C at C. (1;)

Example:

an; f: l: 5:5; 2 1,?rdiaminoethane 0.085 800/26 s Bis-(2-aminoethyl)-amine 0 05 1; jg; 4 1 {3-104 2'000 31 5148 s 1,11-diamin0- ,6,9-triazaundecane.-. 0.1 {fiI ggg 4. 60 6 fi a an. 0 23 {$32 233% 2g 7 'd1am1 0butane 0.13 700/34 for example phenols or aromatic amines, such as 2,6-di- From 0.05 to 0.8% by weight of a secondary amine y P Y Y- whose organic radicals contain at least 10 carbon atoms g'gi R F fmethane or Y 40 may a so be added to the deactivator solution in order .1131) t y amme quantmes 0 mm to 2% by welght' to improve the stability of the vulcanisate. This does not EXAMPLES in any way affect the stabilisation, according to the inpolymerisation vention, of cis-1,4-polyisoprene, against degradation during working-up by steam distillation. The secondary amine 2 kg. of isoprene were polymerlsed up to a conversion 1 bl t t d ad d k rate of 93% in 10% by weight solution in n-hexane in on 1 S own 18 E e o prejven egr a 10 u 1 g Wor the presence of an organometallic mixed catalyst compris- P as shown In Table 2 Wlth reference to the example of ing TiCl and Al(C H methyl stearylamine.

TABLE 2 I Solution Quantity, Defo viscosity percent ML-4'/ HIE, in toluene Amine by weight 100 C. 80 C. at 25 C 1;

Example: 7

7 Methylstearylamine {32:32 igggfig 2 8 Bis-(Z-aminoethyD-amine 0. 1 2:2; 11-94 1.950137 5.58 9 g g gggg 'm 5 {13-94 1,950 37 5.88

Workingmp The process described 'in' this specification not only prevents the degradation of cis-1,4-po1yisoprene during its InlXtllfe 0f 10% y Weight of c, 2.5% by isolation'from hydrocarbon solutions by distillation with weight of ethanol and 1% by weight of 2,6-d1-tert.-buty1- steam, but also improves the stability of the polymers '4-methylphenol (based on polyisoprene), was added to in storage.

The data set out in Table 3 shows that, even. after storage for 90 days at room temperature (25 C.), the polymers worked-up inaccordancewith the invention do not show any reduction in their Mooney and Defo values by weight of ethanol in solution in 1.0% by weigh of and TABLE 3 Storage Defo at room Percent Percent ML-4l H/E tempera- Deactivator by weight stabllizer by weight 100 C. 80 C. Working-up turo, days Example No.: 93 2, 050/25 5 Ethanol 2,6-d1-tert.-butyl-4- 1.0 86 1, 000/22 Ethanol precip., 5 methyl phenol. 77 800/14 steam-distillation. 90 Bis-(Z-aminoethyD- 0.1 100 2,150 5 11 amine. .---.do 1.0 100 2,150/33 do s Ethanol 2.5 102 2,100/35 90 Bis-(2-aminoethyl)- 1.0 103 2,100 30 5 12 amine. -d0 1.0 100 2,160/30 do 5 Methylstearylamine- 0.5 100 2, 000/32 90 Ethanol 2.5 100 1, 900 30 5 13 --{Methylstearylamine. 0.5 }.....do 1.0 91 1,450/23 do 5 Ethanol 2.5 88 1,175/27 90 14 Ethanol 2.5 2,2-dihydroxy-3,3-di- 101 1, 900 32 5 tert-.butyl-5,5-di- 0.5 92 1, 1500/25 do 5 methyl diphenyl 78 850/15 90 methane. 104 1, 900 30 5 Ethanol 2.5 2,2-dil1ydIoXy-3,3'- 0.5 82 1, 450/20 do 5 15 di-tert.-5,5-dimethyl 72 700 14 90 Methylstearylamine.-. 0. diphenylmethane. 98 2,100/36 5 Ethanol 2.5 0.5 101 2, 200/ do 5 16 Bis(2-aminoethyl)- 0.2 ..do 100 2,150/35 90 amine.

The working up process according to the invention also based on the Weight of the polyisoprene, is added to said considerably improves hot-air ageing. Table 4 shows the solvent solution. Mooney viscosity data after storage for 7 days in a Greer 3. The process of claim 1 wherein said primary or oven at 70 C. The conventional anti-ager, 2,2-dihydroxy- 25 secondary polyalkylamine and said aliphatic secondary 3,3-di-tert.-butyl-S,S-dimethyl-diphenylmethane, was used monamine are added to said solvent solution as a soluin a small quantity (0.2% by Weight) in this test 1n order tron in a hydrocarbon solvent. to show up the elfect of bis-(2-aminoethyl)-amine. 4. The process of claim 3 wherein said organic solvent TABLE 4 Mooney viscosity. Percegit Percegit ML-4'/100C Y Y Deaetivator weight Stab1hser weight a b Example N0.

17 Ethanol 2 5 2,2-d1hydroxy-3,3-terti-butyl-5,5'- 0,2 93 63 h 1 2 5 dimethyl-diphenyl-methane. Et ano 18 iggfl-afninoethyb-amine 2 98 77 2110 19 --{Bis-(2-aminoethyl)-amine 0. 2 2 94 80 Methylstearylamine 0. 4

NoTE.-a=measured after working up; b=after 7 days in a Geer oven at 70 C. What is claimed is: of said polyisoprene solution corresponds to the hydro- 1. A process for isolating cis-l,4-polyisoprene from Carbon solvent for said amines. its polymerisation solution in an organic solvent containing organo-metallic mixed catalyst, said process com- References Clted prising deactivating said catalyst by adding to said solu- UNITED STATES PATENTS i011 0.02 to 1.00% by weight, based 0D. the Weight of 3 00 944 11 1961 il 2 0 943 the polyisoprene, of a pri a y or secondary polyalkyl- 3:135:716 6/1964 Uraneck 260 45 s amine containing up to 6 carbon atoms in said alkyl 3,269,997 8/1966 Lyons et 5; moieties and 0.05 to by Weight, based on the 3,165,503 1/1965 Kahn et a1 26094 3 weight of said polyisoprene, of an aliphatic secondary 3,424,735 1/1969 gaf monoamine having methyl as one nitrogen substitutent and alkyl containing 9 to 24 carbon atoms as the other JOSEPH L. SCHOFER, Primary Examiner nitrogen substitutent and then steam distilling said mix- W. R HAMROCK Assistant Examiner ture.

2. The process of claim 1 wherein a lower aliphatic US. Cl. X.R. alcohol in an amount of from 0.05 to 5% by weight, 260-85.1 

